CN101980782A - Colloidal titanium dioxide sols - Google Patents

Colloidal titanium dioxide sols Download PDF

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CN101980782A
CN101980782A CN200880128408XA CN200880128408A CN101980782A CN 101980782 A CN101980782 A CN 101980782A CN 200880128408X A CN200880128408X A CN 200880128408XA CN 200880128408 A CN200880128408 A CN 200880128408A CN 101980782 A CN101980782 A CN 101980782A
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tio
sol
titanium dioxide
titanium
colloidal sol
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G·付
B·M·蒙克
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Millennium Inorganic Chemicals Ltd
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Millennium Inorganic Chemicals Ltd
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Priority to CN201510090443.9A priority Critical patent/CN104761931A/en
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Abstract

Stable, translucent or transparent titanium dioxide sols comprising amorphous titanium dioxide and an organic peptizing agent are provided that are useful in particulate binding applications. Also provided are methods for preparing the inventive sols. The inventive sols are prepared from titanium dioxide precursors including organotitanium compounds and water-soluble titanium salts that are treated to precipitate amorphous titanium dioxide. The amorphous titanium dioxide is re-dispersed and peptized to form a translucent or transparent mixture. The inventive sols are stable for an extended period of time.

Description

Colloidal titania colloidal sol
Technical field
The present invention relates to stable colloidal titania colloidal sol and prepare the method for these colloidal sols.More specifically, the present invention relates to comprise the stable and transparent TiO 2 sol of amorphous titania.
Background technology
In many application, need particle binders that each component is kept together (in order to improve machinability, mechanical stability, adhesion property) and strengthen the performance of described component.For example, U.S. Patent No. 4,317,778,4,351,773 and 4,374,043 describes phosphoric acid vanadium (VPO) Preparation of catalysts that is used for the hydrocarbon oxidation, wherein uses the bonding VPO particle of silicon dioxide gel to improve the wearability of this catalyst.
In some surface-coated with in print using, use particle binders to strengthen to apply or print the mechanical stability of member and member adhesion to substrate surface.
Silica (SiO 2) rather than titanium dioxide typically be used for these application.Reason may be the normally amorphous and titanium dioxide of a silica dioxide granule crystalline material typically.Amorphous granular is characterised in that the hydroxyl that contains high concentration from the teeth outwards, and it provides a lot of active sites on the surface of particle, produces other surperficial strongly bonded.On the contrary, titanium dioxide typically exists as the crystalline solid that has than the low adhesion energy.
Yet, in bonding application, advantageously use titanium dioxide rather than silica.For example, chemically more stable, and titanium dioxide is photoactive and has bigger catalytic activity titanium dioxide than silica.For this reason, titanium dioxide is used for the wherein useful surface-coated application of photocatalysis performance.
Commercial titanium dioxide is produced with two kinds of crystalline phases typically, i.e. rutile that lattice structure, refractive index and density are different and anatase.Rutile is more stable phase and is advantageously used in pigment applications that this is because rutile pigment is compared with their anatase homologue and had higher refractive index, causes bigger opacity and whiteness mutually.
The anatase form of titanium dioxide is compared the normal light activity and is used for photocatalytic applications more greatly and typically with rutile form.When being exposed to the light time, Photoactive titania forms reactive materials, and this material can make the NO that contacts with catalysis material xAnd VOC (VOC) degraded.In view of these performances, in coating, use photocatalysis titanium dioxide from environment, to remove pollutant.Because oxidation dirt (grease, mould, mould, algae etc.) from the teeth outwards also, such coating can also have self-cleaning advantage.
The U.S. Patent Application Publication No.2004/0241502 of Chung etc. (incorporating this paper by reference into) has described neutral and transparent colloidal tio 2 colloidal sol and has made the method for described colloidal sol.It is anatase form that the disclosure has disclosed the titanium dioxide granule that uses in the colloidal sol.Described colloidal sol contains the titanium dioxide of the 1-5% of mixture weight.
The U.S. Patent No. 6,824,826 (incorporating this paper by reference into) of Amadelli etc. has been described colloid TiO 2Preparation, described colloid TiO 2Can be doped be selected from I-VA family, group of the lanthanides and actinium series metal in order on the stone and marble product that are coated in the cement shape.Colloidal titania is passed through TiO 2The hydrolysis of precursor in rare nitric acid prepares.
The U.S. Patent No. 6 of Ohmori etc., 627,336 (incorporating this paper by reference into) were described a kind of aqueous dispersion of titanium dioxide in small, broken bits, and this dispersion comprises chlorion and at least a Bronsted alkali that is selected from pyrophosphate, metaphosphate, Quadrafos, methane sulfonates, ethane sulfonate, dodecyl benzene sulfonate and propane sulfonate.
The U.S. Patent No. 6,737,485 (incorporating this paper by reference into) of St.Clair etc. has been described stabilized dispersion that is formed by the titanium chelate polymer and the method for preparing the stabilized dispersion of this titanium chelate polymer.Make this dispersion stable by the various stabilisation compounds that comprise carboxylic acid.
The U.S. Patent No. 6,420,437 (incorporating this paper by reference into) of More etc. discloses thinks the neutral colloidal tio 2 colloidal sol that has high stability and can form colourless transparent coating in the neutral pH scope.
Therefore, have the demand to stable and the translucent or transparent TiO 2 sol that comprises amorphous titania, described amorphous titania is with the excellent stability of titanium dioxide and the amorphous solid bond properties of photocatalytic activity and expectation.
List the essence that aforementioned discussion only is used for understanding better problem that this area faces, in any case aforementioned discussion can not be interpreted as and admit to be prior art, any document of being quoted can not be interpreted as admitting that these documents constitute the application " prior art " herein.
Summary of the invention
The colloid solution that comprises the amorphous titania with excellent adhesiveness energy is provided, and this colloid solution is used for comprising as surface coating formulations and is printing many application of using.This colloidal sol is transparent or semitransparent and stable over a long time.This paper also provides the method that is used to prepare TiO 2 sol of the present invention.
The stable colloidal titania colloidal sol that comprises the amorphous titania particle is provided.In one embodiment, colloidal sol of the present invention comprises titanium dioxide granule, organic gel solvent and the aqueous solvent of average grain diameter less than 50nm, and wherein this colloidal sol is translucent or transparent; And wherein this colloidal sol is room temperature and 2-8 ℃ of following stablizing 1 month at least.In some embodiments, colloidal sol stable at least 2,3 or 4 months.Preferably, colloidal sol will stablize at least 5 or 6 months.In other embodiments, colloidal sol is room temperature and 2-8 ℃ of following stablizing 1 year or 2 years at least.In one embodiment, the titanium dioxide in the colloidal sol of the present invention is amorphous forms greater than 95 weight %.In another aspect of this invention, the crystal form that does not have titanium dioxide in the titanium dioxide.In preferred embodiments, the titanium dioxide granule in the colloidal sol of the present invention has less than 10nm or preferred average grain diameter less than 5nm.
In one embodiment, the organic gel solvent in the colloidal sol of the present invention be single-, two-or trialkylamine base.The alkyl of amine alkali can be the alkyl of linearity or side chain.Amine alkali comprises tert-butylamine, triethylamine, isopropylamine, diisopropylethylamine (diisopropoylethylamine), isobutyl amine and iso-amylamine.
In another embodiment, TiO 2 sol is included as the organic gel solvent of carboxylic acid, and described carboxylic acid comprises alpha-hydroxy carboxylic acid compounds, beta-hydroxycarboxylic acids or alpha-amino carboxylic acid.Exemplary carboxylic acid peptizing agent comprises lactic acid, tartaric acid, malic acid, citric acid and glycolic acid.
Colloidal sol of the present invention typically comprises the titanium dioxide of the about 25 weight % of about 1%-.In some embodiments, colloidal sol comprises the titanium dioxide of the about 15 weight % of about 5%-, the titanium dioxide of the about 12 weight % of preferably about 8%-.
The method that is used to prepare the stable and transparent or semitransparent colloidal titania colloidal sol that comprises amorphous titania also is provided, and this method comprises:
(i) make the titanium dioxide precursor hydrolysis to form the amorphous titania particle of average grain diameter less than 50nm;
(ii) separate amorphous titania particle from step (i);
(iii) in liquid medium again dispersion steps amorphous titanium particle (ii) to form dispersion; And
(iv) form transparent or semitransparent colloidal sol up to this dispersion with organic gel solvent treatment step dispersion (iii).
In one embodiment, titanium dioxide precursor is four alkoxy titanium compounds, comprises tetraisopropoxy titanium, positive propoxy titanium, four titanium n-butoxide, purity titanium tetraethoxide and tetramethoxy titanium.
In another embodiment of this method, titanium dioxide precursor is water-soluble titanium dioxide titanium salt.When titanium dioxide precursor is water-soluble titanium dioxide titanium salt, this method also be included in make spent ion exchange resin treatment of water-soluble titanium dioxide titanium salt before the titanium dioxide precursor hydrolysis solution so that this solution deionization.
Can handle titanium dioxide precursor with alkaline chelator before the hydrolysis.This alkaline chelator can be a for example triethanolamine of two alkanolamines or trialkanolamine.
In one aspect of the invention, the amorphous titania particle is amorphous forms greater than 95 weight %.Perhaps, the crystal form that does not have titanium dioxide in the amorphous titania particle.Preferably, the amorphous titania particle has less than 10nm or less than the average grain diameter of 5nm.
Aspect of this method, peptizing agent be single-, two-or trialkylamine, the alkyl that it can contain linearity or side chain comprises tert-butylamine, triethylamine, isopropylamine, diisopropylethylamine, isobutyl amine and iso-amylamine.
In another embodiment, the organic gel solvent that uses in the inventive method is a carboxylic acid, comprises alpha-hydroxy carboxylic acid compounds, beta-hydroxycarboxylic acids or alpha-amino carboxylic acid.Special carboxylic acid peptizing agent comprises lactic acid, tartaric acid, malic acid, citric acid and glycolic acid.
The method that forms colloidal sol of the present invention can also comprise with acid or alkali regulates the pH of this colloidal sol to required pH.The inventive method produces the colloidal sol of the present invention that comprises amorphous titania, and these colloidal sols are translucent or transparent and stable over a long time.
Will be by understanding these and other aspect of the present invention better with reference to following the detailed description and the accompanying drawings.
The specific embodiment
The invention provides and comprise amorphous TiO 2Colloidal titania colloidal sol, these colloidal sols are translucent or transparent and stable over a long time.Colloidal sol of the present invention is used for various bonding application and comprises as particle binders, is used for the surface-coated application and is used for printing application.
Titanium dioxide is compared with other adhesive material and not too is usually used in bonding application, and this is because it exists with crystal form rather than as amorphous solid usually.For example, more often use SiO 2As the particle binders in the catalyst application.Therefore amorphous solid contains the surface hydroxyl of high concentration and has and is used for bonding purpose exhibiting high surface active group.Yet titanium dioxide compares SiO 2Chemically stablizing more, be photoactive and compare SiO 2Catalytic activity is bigger, and this is effective in some applications.Therefore, the stable and transparent colloidal sol that comprises amorphous titania of the present invention is very effective in many application.
Some publications have been described the TiO as the dispersion of titanium dioxide in liquid medium 2Colloidal sol, wherein this dispersion is not translucent or transparent.The difference of TiO 2 sol of the present invention and these dispersions is that they are fully transparent or translucent in over a long time.Colloidal sol of the present invention stable at least 1 month and in mixture, do not form noticeable solid usually.Typically, this colloidal sol is in room temperature and 2-8 ℃ stable at least 2 months or 3 months and do not have solid to form down.More typically, this colloidal sol is stable at least 4 months, 5 months or 6 months.In some embodiments, this colloidal sol is in room temperature or 2-8 ℃ stable at least 1 year or 2 years and do not form noticeable solid in mixture down.
Definition
Unless have explanation is arranged in addition, all terms used herein have their its ordinary meaning.
Term " alkyl " is intended to have its conventional sense, comprise straight chain, side chain or ring-type primary, the second month in a season or tertiary hydrocarbon.
Term " aryl " is intended to have its conventional sense, comprise any stable monocyclic, bicyclic or tricyclic carbocyclic ring that comprises 8 yuan at the most (being generally 5 or 6) in each ring, wherein at least one ring has the armaticity by Huckel 4n+2 rule definition, comprises phenyl, xenyl or naphthyl.
Term " heteroaryl " is intended to have its conventional sense, comprises the hetero-aromatic ring group with 5-14 unit.
Term used herein " titanium dioxide precursor " is meant and forms any type of TiO when comprising titanium and carrying out described treatment step 2Any compound.
Term used herein " stable TiO 2Colloidal sol " be meant the TiO that does not form tangible solid between the storage life or performance is significantly changed 2Colloidal sol, described performance comprises the outward appearance that it is translucent or transparent.The stability of visual definite colloidal sol.
Term " room temperature " is intended to be meant 20-25 ℃ temperature range.
By being prepared as follows TiO 2 sol of the present invention: form average grain diameter and be the titanium dioxide granule of amorphous form, then the titanium dioxide of this precipitation of dispersion and handle this mixture to form translucent or transparent mixture in liquid medium with peptizing agent less than about 50nm preferred.
Prepare the amorphous titania particle of average grain diameter less than about 50nm by any suitable intermediate processing in first step, it is including, but not limited to TiO 2The hydrolysis of precursor, the pH adjusting of water-soluble titanium salt and the introducing of anti-solvent.At TiO 2Restricted T iO not before the precipitation 2The concentration of precursor solution is as long as be converted into TiO 2And generate the TiO of required particle diameter and form 2This precursor remains in the solution before the particle.In preferred embodiments, TiO 2The control hydrolysis of precursor compound in aqueous solvent forms the amorphous TiO of appropriate particle size 2Aqueous solvent comprises and contains water so that TiO 2The precursor hydrolysis also produces TiO 2Any suitable solvent or solvent mixture.Typically, can make water or use be mixed with a small amount of organic solvent separately to promote the deliquescent water of titanium dioxide precursor.The mixture of water and organic solvent can also be used to control TiO 2The hydrolysis rate of precursor and TiO 2Precipitation.If with an organic solvent, this solvent is can be typically miscible or can have enough dissolubilities for water and make and can utilize enough water so that TiO with water 2Precursor is hydrolyzed to TiO 2Appropriate organic solvent comprises alcohol for example methyl alcohol, ethanol, isopropyl alcohol etc.; Acid amides is dimethyl formamide and dimethylacetylamide etc. for example; And sulfoxide dimethyl sulfoxide (DMSO) for example.
In some embodiments, with TiO 2Precursor mixes with organic solvent is for example pure, and adds entry to realize TiO 2The hydrolysis of precursor.Along with TiO 2The precursor hydrolysis, it forms as the amorphous TiO of average grain diameter less than about 50nm 2The TiO of solids precipitation 2In another embodiment, with TiO 2Precursor mixes the titanium material that forms chelating with chelating alkali, then this mixture is added to the water so that TiO 2The precursor hydrolysis also is settled out amorphous TiO 2
In one embodiment, TiO 2Precursor is an organic titanic compound.Suitable organic titanic compound is Ti (OR) including, but not limited to general structure 4Alkoxytitanium, wherein each R is alkyl, aryl or heteroaryl independently; The titanium acyl compounds is titanyl acetylacetonate etc. for example.Preferred alkoxytitanium comprises tetraisopropoxy titanium, four positive propoxy titaniums, purity titanium tetraethoxide, tetramethoxy titanium, four titanium n-butoxide and tert-butoxy titanium etc.The alkoxytitanium that is also contemplated to mix (Ti (OR) wherein 4In the R group can be different) as TiO of the present invention 2Precursor.Other suitable organic titanic compound comprises titanium (IV) amines for example four (dimethylamino) titanium, four (diethylamino) titanium etc.As mentioned above, make organic titanium TiO by the water of introducing minimum 2The precursor hydrolysis, this makes and be settled out TiO from solution 2Particle.Depend on employed method, can at first handle organic titanium TiO with chelate compound 2Precursor also mixes it to realize the hydrolysis of this precursor, perhaps only with organic titanium TiO then with aqueous solvent 2Precursor is introduced the solution with organic solvent and then it is mixed with aqueous solvent to form TiO 2
Can also use formula TiX 4The halogenated titanium (wherein X is chlorine, bromine, iodine or fluorine or their mixture) of expression is as TiO 2Precursor.The present invention also anticipates and uses for example three isopropoxy titanium chlorides (Ti (O-i-Pr) of organic titanium halide 3Cl) etc. as TiO 2Precursor.Also anticipate organic titanium two-and three-halide.Though not bound by theory, when using halogenated titanium as TiO 2During precursor, typically at first make this halide be hydrolyzed to for example titanium oxyhalide (being titanium oxychloride etc.) of reactive less material with control mode.Can make gained middle titanium material further be hydrolyzed to TiO then by the pH of regulator solution 2
In another aspect of the present invention, TiO 2Precursor can be water-soluble titanium salt.Suitable titanium salt is including, but not limited to titanium oxychloride, titanyl sulfate, titanyl nitrate etc.Can be adjusted to water-soluble titanium salt by pH hydrolysis is formed TiO solution 2The pH of (it is settled out from solution) realizes being settled out TiO by this water soluble salt 2Typically, this can raise the pH of solution to realize by adding alkali.
Can use any alkali of the pH of known the improved water-soluble titanium saline solution of those skilled in the art to precipitate TiO 2, comprise inorganic base and organic base.Suitable alkali comprises ammonium hydroxide including, but not limited to amine alkali, single-, two-or trialkylamine for example triethylamine, diisopropylethylamine etc.; Cyclic amine alkali is N-ethylmorpholine, piperidines, pyrrolidines etc. for example; The hydroxide of alkali metal or alkaline earth element or alkoxide be the hydroxide of sodium, lithium, potassium for example, magnesium hydroxide, calcium hydroxide; The alcoxylates of sodium, lithium or potassium is methoxylation thing, ethoxylate, butoxy thing, tert-butoxy thing etc. for example; The carbonate of the saline and alkaline for example sodium of carbonate and bicarbonate, lithium or potassium and bicarbonate etc.To be apparent that for the technical staff type of alkali is not limited to above-mentioned alkali and has many other alkali that can be used to regulate the pH of water-soluble titanium salting liquid.
Perhaps, can make TiO by the composition that changes solvent 2No longer solvable and from solution, be settled out TiO 2In this embodiment, can be with the TiO in the solution in suitable solvent 2Precursor joins in second insoluble " the anti-solvent " of precursor wherein.For example, this can be by will be at the miscible organic solvent of the water TiO in acetone or the higher alcohol for example 2Precursor is added to the water and realizes.Perhaps, can join water-soluble TiO by the organic solvent that water is miscible 2In the aqueous solution of salt to reduce TiO 2Dissolubility finish precipitation.The titanium sediment that forms can be used for the next procedure of this method, and no matter its partial hydrolysis or complete hydrolysis are TiO 2
Of the present invention aspect some, at TiO 2Precursor hydrolysis and TiO 2Before the precipitation, by handling TiO with chelating agent 2Precursor is realized TiO 2The control hydrolysis of precursor or control precipitation, described chelating agent forms the stable chelated key with titanium in the aqueous solution.When using chelating agent, can control TiO 2Hydrolysis or the settling rate of precursor in water, thereby the TiO that control forms 2Particle grain size.Can use and in aqueous medium, to form any chelating agent of stablizing chelate bonds, comprise neutral organic compound and organic acid or organic base with titanium.
Typically, the compound that belongs to good chelating agent comprise two or more can with the functional group of titanium chelating.Suitable neutral chelating agent comprises dicarbonyl compound for example diketone, diester, keto ester etc.The diketone chelating agent comprises 2,4-pentanedione, 1,4-acetyl butyryl, 1,3-pentanedione, 2,4-acetyl butyryl and dipivaloylmethane.The diester chelating agent comprises the list or the two-Arrcostab of dicarboxylic acids.Suitable diester comprises dialkyl malonate, for example malonic acid dimethyl esters and malonic acid diethyl ester etc.The keto ester chelating agent is including, but not limited to Acetacetic acid alkyl ester, for example methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, butyl-acetoacetate etc.Can also use the mixture of two or more dicarbapentaborane chelating agents to prepare colloidal sol of the present invention.
Except that dicarbonyl compound, the compound that comprises two kinds of different functional groups of next-door neighbour on a part also is suitable chelating agent.The example of the chelate compound of these types comprises 'alpha '-hydroxy acids and a-amino acid.When chelating agent is chirality, can uses arbitrary enantiomer of chipal compounds or can use racemic mixture.Suitable 'alpha '-hydroxy acids is including, but not limited to lactic acid, tartaric acid, malic acid, citric acid etc.Can use any natural generation or synthetic a-amino acid to prepare colloidal sol of the present invention.For example, can use the L-a-amino acid of 20 kinds of natural generations.Can also use corresponding D-a-amino acid or D, the L-racemic mixture.Anticipate also that for the present invention use has the synthesizing amino acid of non-natural side chain.
The alkali chelating agent comprise contain two or more can with the organic base of the functional group of titanium atom chelating.Suitable chelating agent comprises two alkanolamines and trialkanolamine for example diethanol amine, triethanolamine etc.Other suitable chelating alkali with two or more functional groups comprises ethylenediamine, diethylenetriamines, trien, 2,2 '-bipyridyl, 1,10-phenanthroline, ethylenediamine tetra-acetic acid or ethylenediamine tetraacetate, ethylenediamine triacetic acid or ethylenediamine triacetic acid ester, 2,2 '; 2 "-terpyridyl, 1,4,7-7-triazacyclononane, three (2-amino-ethyl) amine etc.
Use in the embodiment of organic acid as peptizing agent, at one at TiO 2TiO before the precipitation 2Precursor chelating agent of no use is handled.
In another embodiment, when using organic base, at TiO as peptizing agent 2TiO before the solids precipitation 2Precursor is typically handled with suitable organic base chelating agent that can the chelating titanium.Precipitation is before to TiO 2Precursor adds chelating alkali will produce more stable material, and will reduce the peptization of titanium particle in hydrolysis degree and the promotion next procedure.In one embodiment, be used to handle TiO 2The alkali of precursor is identical with the alkali that is used as peptizing agent.Preferably, join TiO 2The amount of the chelating alkali in the precursor makes the mol ratio of alkali and titanium≤0.5: 1.In other embodiments, the mol ratio of alkali and titanium≤0.3 or 0.2: 1.
When using the solubility titanium salt as TiO 2Precursor and when using organic base as peptizing agent typically used the deionization step to reduce before settling step and is present in TiO 2The concentration of the ion in the precursor.The concentration that reduces effects of ion helps the chelating of titanium and chelating agent.Can use any method of the ion concentration that can reduce in the soluble titanium salting liquid, comprise with anion exchange resin process, the precipitation etc. of dissolved salt not.In one embodiment, depend on the character of soluble titanium precursor salt, use anion exchange resin process TiO 2Precursor solution can be at TiO to remove 2Excess amount of ions in the precursor solution is sulfate ion, chlorion etc. for example.When spent ion exchange resin processing soluble titanium salt solution, the pH of this solution typically improves along with the time and can cause forming TiO 2Sediment.Preferably, restriction makes the pH of solution maintain less than about 3 to prevent TiO with the time of anion exchange resin process solubility titanium salt 2Sedimentary formation.More preferably, can limit the deionization processing makes the pH of solution maintain less than about 2.In case reduce the level of ion, just from ion exchange resin, isolate titanium salt solution and use the alkali that can form chelate bonds to handle it by mentioned above.Regulate the pH of titanium dioxide salting liquid of chelating to form TiO with suitable alkali then 2(it is settled out from solution).
The TiO of precipitation 2Can collect by any suitable method that comprises decant, centrifugation and filtration.Before the peptization step, can choose solid byproduct and other impurity that washes separation with water wantonly to remove hydrolysis.
In next procedure, the precipitation TiO of amorphous form will be preferably 2In liquid medium, disperse and handle to form colloidal sol of the present invention with peptizing agent along with stirring.The TiO that disperses 2Can be under the temperature of room temperature or rising form transparent or semitransparent mixture along with stirring to handle up to this dispersion with peptizing agent.The temperature that raises is quickened peptization course usually.Preferred room temperature when peptizing agent is organic base, and when peptizing agent is organic acid, typically use the temperature of rising.When carrying out peptization course at elevated temperatures, typically use about 30 ℃-Yue 100 ℃ temperature range.More typically, the peptization temperature is about 40 ℃-Yue 100 ℃ or about 60 ℃-Yue 100 ℃.
TiO 2Concentration in dispersing liquid will determine the initial concentration of colloidal sol behind the peptization.Certainly, if desired, after finishing the peptization step, can further dilute or concentrated TiO of the present invention 2Colloidal sol.Typically, have the about 30 weight %TiO of about 1 weight %-in the aqueous solvent 2TiO 2Dispersion will be used for the peptization step.Aqueous solvent can be any solvent or the solvent mixture that comprises water.For example, can make for example mixture of alcohol of the miscible solvent of water and water.More typically, the concentration of dispersion is the about 15 weight % of about 2 weight %-or the about 15 weight % of about 5 weight %-of mixture.Preferably, concentration is about 12 weight % of about 8 weight %-or the about 10 weight % of about 5 weight %-.
Many organic acids and organic base are suitable for as peptizing agent of the present invention.Preferred Aci-Jel solvent comprises the carboxylic acid with the replacement of one or more functional groups, and described functional group is including, but not limited to hydroxyl, alkoxyl, amino, list-or dialkyl amido, carboxyl, carboxylate, carbamyl, amino, urea, mercaptan, sulfide, disulphide, sulfoxide, sulfone etc.Preferably, the carboxylic acid peptizing agent can with second functional group α-or β-carbon replace.These peptizing agents are including, but not limited to alpha-hydroxy carboxylic acid compounds, beta-hydroxycarboxylic acids, alpha-alkoxy yl carboxylic acid and alpha-amino carboxylic acid.When chelating agent has asymmetric carbon and is chirality, can use arbitrary enantiomer of chipal compounds or can use racemic mixture.
Preferred alpha-hydroxy carboxylic acid compounds is including, but not limited to lactic acid, tartaric acid, malic acid, citric acid, glycolic acid, 2-hydroxy-iso-butyric acid, 2-hydroxy-2-methyl butyric acid, 2-ethyl-2-hydroxybutyric acid, 2-hydroxy-3-methyl butyric acid, 2-hydroxyl isocaproic acid, 3-hydroxybutyric acid, 2, two (methylol) propionic acid of 2-, citramalic acid, 3-hydroxy-3-methylglutaric acid, gluconic acid, 2-isopropylmolic acid, glutinous acid, succinic acid (dihydrofumaric acid), chinic acid, methoxyacetic acid (methoxyacetic acid), ethoxyacetic acid etc.
Can use any natural generation or synthetic a-amino acid to prepare colloidal sol of the present invention.For example, can use the L-a-amino acid of 20 kinds of natural generations.Can also use corresponding D-a-amino acid.Anticipate also that for the present invention use has the synthetic alpha-hydroxy carboxylic acid compounds and the a-amino acid of non-natural side chain.
Many alkaline peptizing agents can be used for the present invention, comprise single-, two-or trialkylamine; Single-, two-or tri-arylamine group; Organic base with two or more functional groups is two alkanolamines and trialkanolamine etc. for example.Single-, two-or the trialkylamine peptizing agent can comprise linearity, side chain or cyclic alkyl.Suitable amine including, but not limited to single-, two-or Trimethylamine; Single-, two-or triethylamine; Single-, two-or tripropyl amine (TPA); Single-, two-or tri-butylamine, sec-butylamine, isobutyl amine, isopropylamine, iso-amylamine, uncle's amylamine, 2-methylbutylamine, 1-methylbutylamine etc.Amine with cyclic alkyl comprises two of cyclopropylamine, ring butylamine, cyclopentamine, cyclohexylamine, cycloheptylamine and cyclooctylamine and they-and three-alkyl derivative.Certainly, can use amine for example diisopropylethylamine, ethyl butyl amine, methyl ethyl-amine etc. with different alkyl.What also anticipate is for example pyrrolidines, piperidines, morpholine etc. and their N-alkyl derivative of cyclic amine.Preferably, use the list of large volume (bulky)-, two-or trialkylamine for example tert-butylamine, triethylamine, propylamine, di-n-propylamine, diisopropylethylamine etc. as alkaline peptizing agent.As mentioned above, when using alkaline peptizing agent, peptization course preferably carries out under room temperature (being intended to be meant about 20 ℃-25 ℃).In other embodiments, the peptization with alkaline peptizing agent carries out at about 20 ℃-Yue 30 ℃ or about 25 ℃-Yue 30 ℃.
At TiO 2After the peptization, can use any normally used inorganic or organic acid or alkali that the pH of this colloidal sol is adjusted to neutral pH or other required pH scope.It is about 6-8 that the colloidal sol that preferably will comprise alkaline peptizing agent remains on pH.It is 3-10 that the colloidal sol that comprises the carboxylic acid peptizing agent typically remains on pH.
Stable and transparent or semitransparent TiO in aqueous solvent 2Colloidal sol contains the TiO of the about 30 weight % of 1 weight %-that have an appointment 2More typically, this colloidal sol can contain the titanium dioxide of about 15 weight % of the 2 weight %-that have an appointment or the about 15 weight % of about 5 weight %-.Preferably, this colloidal sol contains the about 12 weight % of about 8 weight %-of mixture or the TiO of the about 10 weight % of about 5 weight %- 2
In TiO 2 sol of the present invention, any type of titanium dioxide be can use, amorphous form, rutile or anatase form comprised.In addition, the mixture of amorphous form, rutile or anatase form.Preferably, the titanium dioxide granule that uses in the colloidal sol of the present invention preferably is mainly amorphous form.The amorphous form of the titanium dioxide during colloidal sol is used is particularly useful, and this is because TiO 2Amorphous form contain the surface hydroxyl of higher amount, it improves TiO 2The ability of bonding other element (element)." mainly " is meant that the level of the amorphous form of titanium dioxide granule is greater than about 80% in colloidal sol of the present invention, more preferably greater than about 90% or greater than about 95% particle.In some embodiments, the titanium dioxide granule in the composition is essentially pure amorphous form, and the content of expression amorphous form is greater than 97 quality %, and also more preferably, the content of amorphous form is greater than 98 quality %.In some preferred embodiments, can not have the crystal form (comprising rutile and anatase form) of titanium dioxide in the amorphous dioxide particle, expression does not detect crystal form by Laue method.In other words, TiO 2 sol can comprise 100% amorphous titania.Measure degree of crystallinity and crystalline phase character by X-ray diffraction.In the limit of analytical technology, do not exist the known crystal form of titanium dioxide to represent that according to the feature diffraction pattern peak of angle position (2 θ) 100% titanium dioxide is amorphous form.
The average grain diameter of the titanium dioxide that uses in the colloidal sol of the present invention is typically less than about 50nm.More typically, the average grain diameter of titanium dioxide granule is less than about 30nm, 20nm or 10nm.In preferred embodiments, the particle diameter of the titanium dioxide in the colloidal sol can be less than about 5nm.The size of carbon dioxide particle mentioned herein is interpreted as being meant the average grain diameter of titanium dioxide fine particles.When modifying particle diameter by term " about ", be understood to include the particle diameter bigger or more a little bit smaller a little than pointed value, have intrinsic experimental error and have mobility between the distinct methods of measuring particle diameter because measure, this will be apparent to those skilled in the art.Diameter can by standard granularmetric analysis technology for example transmission electron microscopy (TEM) or by light scattering technique (dynamic light scattering, Malvern Instruments Ltd. U.K.) measures.
Perhaps, particle can characterize by surface area.Typically, the titanium dioxide that uses in the colloidal sol of the present invention has greater than about 20m 2The surface area of/g, described surface area can record by any suitable method, comprises the 5-point BET on the drying sample.More typically, photocatalytic titanium dioxide particles has greater than about 50m 2/ g or greater than about 70m 2The surface area of/g.In a more preferred embodiment, titanium dioxide granule has greater than about 100m 2/ g is preferably greater than about 150m 2The surface area of/g.In some embodiments, titanium dioxide granule has greater than about 200m 2/ g is greater than about 250m 2/ g or even greater than about 300m 2The surface area of/g.
Embodiment
List that following embodiment is auxiliary to understand the present invention, and in no case plan and should not be construed as limiting the invention.For the person of ordinary skill of the art, all replacement schemes, modification and the equivalence that will become apparent on the basis of reading disclosure of the present invention is included in spirit of the present invention and the scope.
Embodiment 1
Under gentle agitation, the titanium isopropoxide (IV) (AlfaAesar, 95%) of 3000 grams in big plastic beaker and 600 gram triethanolamines (Alfa Aesar, 98%) were mixed about 15 minutes.This solution becomes during mixed processing warm (warm), shows the formation of titanium-triethanolamine complex.The gained mixture that will comprise titanium-triethanolamine along with vigorous stirring joins second beaker that contains the 15L deionized water with the flow of about 100 gram/minute, produces the TiO of amorphous form 2Precipitation.After adding is finished the gained mixture was mixed other 30 minutes, and allow this mixture leave standstill 48 hours.The upper liquid layer of decant sample then.Along with stirring residual solids was disperseed in water 15 minutes again.At room temperature tert-butylamine (Alfa Aesar, 98%) is joined in the mixture of this dispersion.Along with gentle agitation is stirred this mixture up to finishing peptization and this mixture becomes transparent.Small amount of hydroxyl groups acetate (Alfa Aesar, 70%) is added drop-wise in the mixture of peptization to regulate pH is about 10 to 7.5 along with stirring.
Make about 2 gallons of transparent, yellowish amorphous titania colloidal sols in this way.The concentration of weight analysis determining titanium dioxide is about 10%.Find this colloidal sol stable June at least of pH in 6.5-8 at room temperature and in refrigerator (2-8 ℃).
Embodiment 2
With 150g deionized water dilution 250 gram TiO (SO 4) (Millennium Inorganic Chemicals, 7.9 weight % are with TiO for solution 2Meter).Continuing in this solution, to add 400 gram anion exchange resin (Dowex Monosphere altogether under the stirring with per 5 minutes about 25 gram parts TM550A OH Form).After anion exchange resin adds, stir this mixture and also by filtering solution was separated with resin balls then in other 60 minutes.Then the solution that filters is mixed with 40 gram triethanolamines (chelating agent).In this, this solution is still limpid.Ammonia solution (Fisher, 29%) is joined in this limpid solution lentamente up to pH is about 7 along with stirring, and this causes amorphous TiO 2Precipitation.Allow the gained sediment mix other 30 minutes and filtration then.Solid with the deionized water washing and filtering of about 400g.Wet cake is dispersed in again to reach gross weight in the deionized water be 400g.In this dispersion, add 8 gram tert-butylamines, and slowly stir about 8 hours of this mixture to produce transparent amorphous TiO 2Colloidal sol.With glycolic acid regulate this mixture to pH be 7.5.Make the vitreosol of about 400 grams by this method, it contains the amorphous TiO of 7.5 weight % 2, under room temperature and 2-8 ℃ in stable at least 6 months of the pH of 6.5-8.
Embodiment 3
225 gram titanium isopropoxides (IV) and 225 gram isopropyl alcohols (Fisher, 99.9%) are mixed.Along with vigorous stirring slowly joins this mixture in the water of 1,125 gram, cause sediment to form.Filter this sediment and with about 1200g water washing filter cake 4 times.Wet cake is dispersed in again makes in the deionized water that the gross weight of dispersion is 600g.With 30 gram D, (AlfaAesar 85-90%) joins in this slurry L-lactic acid, and this mixture was added hot reflux 3 hours, and it becomes transparent afterwards.Cooling off gained colloidal sol and with tert-butylamine it being adjusted to pH is 7.Transparent amorphous TiO 2Colloidal sol contains the 10 weight %TiO that have an appointment 2And under room temperature and 2-8 ℃ the stable June at least of pH of 3-10.

Claims (41)

1. stable colloidal titania colloidal sol that comprises titanium dioxide granule, described titanium dioxide granule is dispersed in the aqueous solution that comprises organic peptizing agent; Described titanium dioxide granule mainly is amorphous and has average grain diameter less than about 50nm that wherein said colloidal sol is translucent or transparent and at room temperature stable at least 1 month.
2. the TiO 2 sol of claim 1, the amorphous form of wherein said titanium dioxide is greater than 95 weight %.
3. the TiO 2 sol of claim 1 does not have the crystal form of titanium dioxide in the wherein said titanium dioxide.
4. the TiO 2 sol of claim 1, wherein said titanium dioxide granule have approximately the average grain diameter less than 10nm.
5. the TiO 2 sol of claim 1, wherein said titanium dioxide granule have approximately the average grain diameter less than 5nm.
6. the TiO 2 sol of claim 1, wherein said organic gel solvent be single-, two-or trialkylamine base.
7. the TiO 2 sol of claim 6, wherein said list-, two-or trialkylamine comprise branched alkyl.
8. the TiO 2 sol of claim 6, wherein said amine alkali is selected from tert-butylamine, triethylamine, isopropylamine, diisopropylethylamine, isobutyl amine and iso-amylamine.
9. the TiO 2 sol of claim 1, wherein said organic gel solvent is a carboxylic acid.
10. the TiO 2 sol of claim 9, wherein said carboxylic acid is alpha-hydroxy carboxylic acid compounds, beta-hydroxycarboxylic acids or alpha-amino carboxylic acid.
11. the TiO 2 sol of claim 9, wherein said carboxylic acid is selected from lactic acid, tartaric acid, malic acid, citric acid and glycolic acid.
12. the TiO 2 sol of claim 1, wherein said colloidal sol comprise the titanium dioxide of the about 15 weight % of about 5 weight %-.
13. the TiO 2 sol of claim 1, wherein said colloidal sol comprise the titanium dioxide of the about 12 weight % of about 8 weight %-.
14. the TiO 2 sol of claim 1, wherein said colloidal sol at room temperature stable at least 3 months.
15. the TiO 2 sol of claim 1, wherein said colloidal sol at room temperature stable at least 6 months.
16. the TiO 2 sol of claim 1, wherein said colloidal sol at room temperature stable at least 1 year.
17. the TiO 2 sol of claim 1, wherein said colloidal sol at room temperature stable at least 2 years.
18. the TiO 2 sol of claim 1, wherein said colloidal sol was stablized 1 month down at 2-8 ℃ at least.
19. the TiO 2 sol of claim 1, wherein said colloidal sol was stablized 3 months down at 2-8 ℃ at least.
20. the TiO 2 sol of claim 1, wherein said colloidal sol was stablized 6 months down at 2-8 ℃ at least.
21. the TiO 2 sol of claim 1, wherein said colloidal sol was stablized 1 year down at 2-8 ℃ at least.
22. the TiO 2 sol of claim 1, wherein said colloidal sol was stablized 2 years down at 2-8 ℃ at least.
23. a method that is used to prepare the stable and transparent or semitransparent colloidal titania colloidal sol that comprises amorphous titania, this method comprises:
(i) solution of acquisition titanium dioxide precursor compound;
(ii) make the titanium dioxide precursor compound hydrolysis to form titanium dioxide, wherein titanium dioxide is settled out from described solution as the amorphous titania particle of average grain diameter less than 50nm;
(iii) separate from step amorphous titania particle (ii);
(iv) in liquid medium, form the dispersion of step amorphous titanium particle (iii); And
(the stable and transparent or semitransparent colloidal sol that v) comprises the amorphous titania particle with formation with organic gel solvent treatment step dispersion (iv).
24. the method for claim 23, wherein said titanium dioxide precursor are four alkoxytitaniums.
25. the method for claim 24, wherein said four alkoxytitaniums are selected from tetraisopropoxy titanium, positive propoxy titanium, four titanium n-butoxide, purity titanium tetraethoxide and tetramethoxy titanium.
26. the method for claim 23, wherein titanium dioxide precursor is water-soluble titanium salt.
27. the method for claim 26, this method also be included in make spent ion exchange resin treatment of water-soluble titanium salt before the titanium dioxide precursor hydrolysis solution so that this solution deionization.
28. the method for claim 23 or 27, wherein said titanium dioxide precursor was handled with alkaline chelator before hydrolysis.
29. the method for claim 28, wherein said alkaline chelator are two alkanolamines or trialkanolamine.
30. the method for claim 29, wherein said chelating agent is a triethanolamine.
31. the method for claim 23, the amorphous form of wherein said amorphous titania is greater than 95 weight %.
32. the method for claim 23 does not have the crystal form of titanium dioxide in the wherein said amorphous titania.
33. the method for claim 23, wherein said amorphous titania particle have approximately the average grain diameter less than 10nm.
34. the method for claim 23, wherein said amorphous titania particle have approximately the average grain diameter less than 5nm.
35. the method for claim 23, wherein said peptizing agent be single-, two-or trialkylamine base.
36. the method for claim 35, wherein said list-, two-or trialkylamine comprise branched alkyl.
37. the method for claim 35, wherein said list-, two-or trialkylamine be selected from tert-butylamine, triethylamine, isopropylamine, diisopropylethylamine, isobutyl amine and iso-amylamine.
38. the method for claim 23, wherein said organic gel solvent is a carboxylic acid.
39. the method for claim 38, wherein said carboxylic acid are alpha-hydroxy carboxylic acid compounds, beta-hydroxycarboxylic acids or alpha-amino carboxylic acid.
40. the method for claim 23, wherein said carboxylic acid is selected from lactic acid, tartaric acid, malic acid, citric acid and glycolic acid.
41. the method for claim 23, this method also comprise the pH that regulates colloidal sol with acid or alkali.
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